• Title/Summary/Keyword: [2+2] Cycloaddition

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Ab Initio Study of Mechanism of Forming Spiro-Heterocyclic Ring Compound Involving Si and Ge from Dichlorosilylene Germylidene (Cl2Si-Ge:) and Acetone

  • Liu, Dongting;Ji, Hua;Lu, Xiuhui
    • Bulletin of the Korean Chemical Society
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    • v.33 no.12
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    • pp.4079-4083
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    • 2012
  • The mechanism of the cycloaddition reaction between singlet state dichlorosilylene germylidene ($Cl_2Si=Ge:$) and acetone has been investigated with B3LYP/6-$31G^*$ and B3LYP/6-$31G^{**}$ method, from the potential energy profile, we predict that the reaction has one dominant reaction pathway. The presented rule of the reaction is that the two reactants firstly form a Si-heterocyclic four-membered ring germylene through the [2+2] cycloaddition reaction. Because of the 4p unoccupied orbital of Ge atom in the Si-heterocyclic four-membered ring germylene and the ${\pi}$ orbital of acetone forming a ${\pi}{\rightarrow}p$ donor-acceptor bond, the Si-heterocyclic four-membered ring germylene further combines with acetone to form an intermediate. Because the Ge atom in the intermediate hybridizes to an $sp^3$ hybrid orbital after the transition state, then, the intermediate isomerizes to spiro-heterocyclic ring compound involving Si and Ge (P4) via a transition state.

The Preparation and Reactions of Some Fluorinated Cyclobutane Carboxylic Acids

  • J. D. Park;F. E. Rogers
    • Journal of the Korean Chemical Society
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    • v.16 no.3
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    • pp.178-188
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    • 1972
  • Diethyl itaconate was found to react tetrafluoroethylene, trifluorochloroethylene, and 1,1-difluoro-2,2-dichloroethylene quite rendily at $180^{\circ}C$ to form 1-carboxy-2,2,3,3,-tetrahalo-cyclobutane ethanoic acid derivatives ${C{\underline{X_2-CF_2-CH_2-}}C-(COOEt)-CH_2COOEt$, where X is Cl or F). Diethylcitraconate failed to yeild any cycloaddition products. The Physical and Chemical properties of the above esters and their dericatives are characterized and compared with other similar ring compounds.

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Heterocyclization Reaction of 4-(2-Methylaziridin-1-yl)-3-ureidobenzotrifluorides under Appel's Conditions

  • Cho, Hyun-In;Lee, Kee-Jung
    • Bulletin of the Korean Chemical Society
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    • v.24 no.2
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    • pp.189-192
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    • 2003
  • The reaction of 4-(2-methylaziridin-1-yl)-3-ureidobenzotrifluorides 4 with triphenylphosphine, carbon tetrachloride, and triethylamine (Appel's condition) led to the corresponding carbodiimides 5, which underwent intramolecular cycloaddition reaction with aziridine under the reaction condition to give the benzimidazolefused heterocycles, 2,3-dihydro-1H-imidazo[1,2-a]benzimidazoles 8 and 12,13-dihydro-5H-benzimidazo[2,3-b] [1,3]benzodiazepines 9.

Synthesis of 3-[1-(t-Butyldimethylsilyloxy)ethyl]-4-carboxymethyl-2-azetidinone Derivatives

  • 서민효;이윤영;구양모
    • Bulletin of the Korean Chemical Society
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    • v.17 no.4
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    • pp.314-321
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    • 1996
  • Isoxazolidine derivatives 7 and 8 were synthesized from N-benzyl-C-(2-benzyloxyethyl)nitrones by 1,3-dipolar cycloaddition with ethyl crotonate. The isoxazolidine derivatives were converted to β-amino acid esters 9a and 9b by reduction with zinc in acetic acid. The β-amino acid esters were reacted with methylmagnesium bromide to give the 2-azetidinones (13a, 13b). The benzyl group of 2-azetidinones were removed by Birch reduction. The products were oxidized with PDC to give 3-[1-(t-butyldimethylsilyloxy)ethyl]-4-carboxymethyl-2-azetidinone derivatives (2a, 2c).

Entry to Highly Hindered Chiral β-Amino Triazoles Bearing a gem-Diaryl Group by Azide-alkyne Click Chemistry

  • Sadu, Venkata Subbaiah;Roy, Harendra Nath;Arigala, Pitchaiah;Hwang, In-Taek;Lee, Kee-In
    • Bulletin of the Korean Chemical Society
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    • v.35 no.6
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    • pp.1605-1612
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    • 2014
  • Copper(I)-catalyzed Huisgen cycloaddition of terminal alkynes with unmasked azidoamines derived from amino acids is described. The reported strategy provides a new entry to highly hindered ${\beta}$-amino 1,2,3-triazole derivatives bearing a gem-diaryl group, which are potentially valuable entities as molecular catalysts for asymmetric transformations.

Synthesis of Polymers Including Both Triazole and Tetrazole by Click Reaction

  • Shin, Jung-Ah;Lim, Yeong-Gweon;Lee, Kyung-Hee
    • Bulletin of the Korean Chemical Society
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    • v.32 no.2
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    • pp.547-552
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    • 2011
  • Azido contained polymers were treated with various substituted N-propargyl tetrazoles in $CH_2Cl_2/H_2O$ at room temperature by Cu-catalyzed [2+3] cycloaddition to afford high yields of the corresponding polymers, possessing both triazole and tetrazole moiety.

Photocycloaddition Reaction of 1,2-Bispyrazylethylene to Tetracyanoethylene

  • Shim, Sang-Chul;Shim, Hyun-Kwan
    • Bulletin of the Korean Chemical Society
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    • v.1 no.4
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    • pp.123-126
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    • 1980
  • Benzene solution of trans-1,2-bispyrazylethylene and electron deficient olefin, tetracyanoethylene, as a ${\pi}$-acceptor gave 1,2-bispyrazyl-3,3,4,4-tetracyanocyclobutane, a 2${\pi}$ + 2${\pi}$ cycloaddition product, on irradiation with 350 nm UV light. Fluorescence studies revealed the reaction to proceed through a singlet exciplex. The fluorescence of trans-1,2-bispyrazylethylene was quenched very efficiently by tetracyanoethylene with the quenching constant of 1.6 ${\times}$ 10$^{10}$M$^{-1}$s$^{-1}$ while electron rich olefin, tetramethylethylene, did not quench the fluorescence of bispyrazylethylene.